EP0756511B1 - Method for fractionating a solution - Google Patents

Method for fractionating a solution Download PDF

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Publication number
EP0756511B1
EP0756511B1 EP95915913A EP95915913A EP0756511B1 EP 0756511 B1 EP0756511 B1 EP 0756511B1 EP 95915913 A EP95915913 A EP 95915913A EP 95915913 A EP95915913 A EP 95915913A EP 0756511 B1 EP0756511 B1 EP 0756511B1
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Prior art keywords
packing material
fraction
column
sectional packing
solution
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German (de)
English (en)
French (fr)
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EP0756511A1 (en
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Heikki Heikkilä
Jarmo Kuisma
Hannu Paananen
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Xyrofin Oy
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Xyrofin Oy
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
    • B01D15/18—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns
    • B01D15/1814—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns recycling of the fraction to be distributed
    • B01D15/1821—Simulated moving beds
    • B01D15/1828—Simulated moving beds characterized by process features
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12F—RECOVERY OF BY-PRODUCTS OF FERMENTED SOLUTIONS; DENATURED ALCOHOL; PREPARATION THEREOF
    • C12F3/00—Recovery of by-products
    • C12F3/06—Recovery of by-products from beer and wine
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C11/00—Regeneration of pulp liquors or effluent waste waters
    • D21C11/0007—Recovery of by-products, i.e. compounds other than those necessary for pulping, for multiple uses or not otherwise provided for
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C11/00—Regeneration of pulp liquors or effluent waste waters
    • D21C11/0042—Fractionating or concentration of spent liquors by special methods
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
    • B01D15/36—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving ionic interaction
    • B01D15/361—Ion-exchange
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2215/00—Separating processes involving the treatment of liquids with adsorbents
    • B01D2215/02—Separating processes involving the treatment of liquids with adsorbents with moving adsorbents
    • B01D2215/023—Simulated moving beds

Definitions

  • the present invention relates to a method for fractionating a solution into two or more fractions enriched with different components.
  • the invention relates to a method for fractionating a solution by a chromatographic simulated moving bed method in which the liquid flow is effected in a system comprising at least two chromatographic sectional packing material beds in different ionic forms, in which the dissolved substances present in the solution are separated from each other, and if the solution to be treated comprises substantial amounts of ions, the system also comprises a unit where the ion equilibrium of the solution is changed.
  • Fractionation of a solution comprising many dissolved substances into fractions enriched with different components is often necessary to recover the desired components as pure as necessary.
  • the method of the invention can be employed to carry out such fractionation.
  • a sulphite cooking liquor for instance, can be fractionated by the method so as to give a fraction rich in monosaccharides and/or a fraction rich in lignosulphonates; furthermore, molasses or vinasse can be fractionated in this way to obtain fractions rich in a sugar, such as sucrose, and/or betaine.
  • the method of the invention is particularly well suitable for recovering monosaccharides from a sulphite cooking liquor, particularly for recovering xylose from a hardwood sulphite cooking liquor, in a continuously operated process by which also a fraction enriched with lignosulphonates can be recovered, if desired.
  • Sulphite cooking liquor in this contest denotes liquor employed in sulphite cellulose cooking, liquor obtained after such cooking, or a part thereof.
  • Finnish Patent 59 388 describes chromatographic separation of polyols, employing columns packed with a cation exchange resin in different ionic forms (resin with a polystyrene skeleton cross-linked with divinylbenzene and activated with sulphonic acid groups).
  • Finnish Patent 69 296 discloses a chromatographic method for the fractionation of polyols, in particular to obtain pure xylitol.
  • this method employs a resin with a polystyrene skeleton cross-linked with divinylbenzene and activated with sulphonic acid groups, packed in parallel columns; in some columns, the resin is in earth alkaline form and in the other columns in Al 3+ or Fe 3+ form.
  • U.S. Patent 4 631 129 discloses the separation of sugars and lignosulphonates from a sulphite spent liquor by a process comprising two chromatographic treatments with ion exchange resins in different ionic forms.
  • the sulphite spent liquor is introduced into a chromatographic column comprising a strong acid resin used as column packing material in metal salt form; the metal ion is preferably a metal ion of the spent liquor, usually calcium or sodium.
  • a substantially sugarless fraction rich in lignosulphonates and a fraction rich in sugars are obtained from this column by elution.
  • the latter fraction is subjected to a softening treatment, and its pH is adjusted to be in the range 5.5 to 6.5, whereafter it is introduced into the second chromatographic column containing resin in monovalent form, and a second fraction rich in sugars and a second fraction rich in lignosulphonates and salts are obtained therefrom by elution.
  • the process is capable of recovering sugars, e.g. xylose contained in hardwood sulphite spent liquor, in a very high purity and high yields.
  • a drawback of the method is that the dry solids profile which has been formed in the first chromatographic treatment and in which the components are already partly separated is destroyed in the softening treatment and pH adjustment and thus cannot be utilized in the second chromatographic treatment.
  • the method is also complicated by the steps of concentration and additional pumping to which the solution is subjected. All of these factors add to investment costs.
  • this method and all prior art chromatographic separation methods in which ion exchange resins of different ionic forms are used are attended by the drawback that they are typically batch methods and are not suitable for fractionating solutions on an industrial scale.
  • the simulated moving bed method enables a separating performance as high as several times that of the batch method, and also significantly lower dilution of the products (consumption of eluent).
  • the simulated moving bed method may be either continuous or sequential, as described in the copending Finnish patent applications 930321 and 932108 (corresponding to international patent applications WO 94/17213 and WO 94/26380, respectively).
  • all flows are continuous. These flows are: supply of feed solution and eluent, recycling of liquid mixture, and withdrawal of products. The flow rate for these flows may be adjusted in accordance with the separation goals (yield, purity, capacity). Normally, 8 to 20 sectional packing material beds are combined into a single loop. The feed and product withdrawal points are shifted cyclically in the downstream direction in the packing material bed.
  • a dry solids concentration profile is formed in the packing material bed.
  • Components having a lower migration rate in the packing bed are concentrated in the back slope of the dry solids concentration profile, and respectively components having a higher migration rate in the front slope.
  • the points of introduction of the feed solution and eluent and the withdrawal points of the product or products are shifted gradually at substantially the same rate at which the dry solids concentration profile moves in the packing material bed.
  • the feed and withdrawal points are shifted cyclically by using feed and product valves located along the packing material bed typically at the upstream and downstream end of each sectional packing material bed. If it is desired to recover product fractions of very high purity, short cycle times and a plurality of sectional packing material beds must be employed (the apparatus has the requisite valves and feed and withdrawal equipment).
  • the flows are: supply of feed solution and eluent, recycling of liquid mixture, and withdrawal of products (eluting phase; 2 to 4 or more products).
  • the flow rates and the volumes of the different feeds and product fractions may be adjusted in accordance with the separation goals (yield, purity, capacity).
  • the method comprises three basic phases: feeding, elution and recycling. During the feeding phase, a feed solution, and possibly also an eluent during a simultaneous eluting phase, is introduced into predetermined sectional packing material beds, and simultaneously a product fraction or fractions are withdrawn.
  • eluent is introduced into a predetermined sectional packing material bed or predetermined sectional packing material beds, and during these phases two, three or even four product fractions are withdrawn.
  • the recycling phase no feed solution or eluent is supplied to the sectional packing material beds and no products are withdrawn.
  • Sequential simulated moving bed methods are disclosed in British published application 2 240 053 and U.S. Patent 4 970 002, for instance.
  • a sequential simulated moving bed method applied to the recovery of betaine and sucrose from beet molasses is disclosed in Finnish Patent 86 416 (U.S. Patent 5 127 957).
  • the above-mentioned copending Finnish patent applications 930321 (filing date January 26, 1993) and 932108 (filing date May 19, 1993) relate to a sequential simulated moving bed method, the first applied to the fractionation of molasses and the latter to the fractionation of sulphite cooking liquor.
  • the simulated moving bed method may be a multi-step process.
  • the object of the present invention is a chromatographic method for the continuous fractionation of solutions, employing ion exchange resins of two or more different ionic forms, so that the dry solids concentration profile formed upon passage of the solution through the chromatographic packing material having a first ionic form is passed to the chromatographic packing material having a second ionic form without the partially separated components being remixed, and/or that the concentration and pumping stages of the solution, included in the prior art methods for fractionating solutions with packing material of two different ionic forms, can be avoided.
  • the method of the invention By the method of the invention, valuable components of solutions produced as by-products in industry, such as monosaccharides and lignosulphonates from sulphite cooking liquor in the pulping industry and sugar, such as sucrose, and/or betaine from molasses produced in the sugar industry or vinasse produced in the fermentation industry, can be advantageously recovered.
  • the method of the invention is particularly suitable for the recovery of xylose from a hardwood sulphite cooking liquor.
  • the present invention relates to a simulated moving bed method in which the liquid flow is effected in a system comprising at least two sectional packing material beds of different ionic forms. Between fractionation operations performed in packing materials of different ionic forms, the solution may be subjected to an additional treatment step. For example, if the solution contains ions, the ion equilibrium of the solution is changed to be suitable for fractionation in the packing material having another ionic form. A change in the pH is also a change in the ion equilibrium.
  • a preferred embodiment of the invention is a sequential simulated moving bed in which the products are recovered during a multi-step sequence.
  • a sectional packing material bed may comprise one column; it is nevertheless also possible to pack several successive sectional packing material beds in a single column, depending on the column structure. On the other hand, several successive columns may be connected to form one or more loops.
  • Changing of the ion equilibrium of the solution to be suitable for fractionation with a packing material having another ionic form may comprise removal of specific ions from the solution by ion exchange or precipitation, pH adjustment, and/or filtration, for instance.
  • the feed solution is sulphite cooking liquor having calcium as the base
  • this can be exchanged into sodium by ion exchange, or the calcium may be precipitated for example as calcium sulphite or calcium sulphate with a sodium sulphite solution or sulphuric acid.
  • the dry solids profile can be maintained essentially intact when the precipitation is performed for example in a tube reactor.
  • the apparatus for carrying out such treatments can be connected in series between the sectional packing material beds having different ionic forms.
  • the ionic form of the packing material in this context means the ion equilibrium; for instance one sectional packing material bed may be predominantly in the calcium form and partly in the magnesium and/or sodium form.
  • the ionic form of the packing material is equilibrated according to the ionic form of the feed solution employed, and/or it is separately adjusted to suit the solution to be treated in each case.
  • the ionic form of the sectional packing material beds is selected in accordance with the solution to be fractionated.
  • the packing material bed for the first fractionation treatment is preferably in the base form of the cooking liquor (often calcium or magnesium) and the packing material bed for the second fractionation treatment in monovalent metal ion form, e.g. Na + and/or K + form.
  • the monovalent form e.g. Na + or K +
  • the divalent form e.g. Ca 2+ or Mg 2+ ).
  • the method of the invention may be employed to fractionate sugar solutions as well. For example from a solution obtained from lactose by alkaline isomerization and containing lactose, lactulose and galactose, a fraction enriched with galactose can be separated with a packing material in Na + form, and fractions enriched with lactulose and lactose can be separated from one another with packing material in Ca 2+ form.
  • salts can be removed from molasses, or maltose can be removed from syrup, with a packing material in K + /Na + form, and after subsequent inversion of sucrose, being carried out as an intermediate step, fractions enriched with glucose and fructose can be separated from one another with a packing material in Ca 2+ form.
  • the product or products are recovered by employing a multi-step sequence comprising the following operations, i.e. phases: feeding phase of the solution to be fractionated, eluting phase and recycling phase.
  • the solution to be fractionated (feed solution) is supplied to the sectional packing material bed, and a corresponding amount of a product fraction is recovered at a point downstream in the flow direction, which may be either in the same sectional packing material bed as the feed point (in which case the other sectional packing material beds in the system may be in the eluting or recycling phase, for instance) or in a sectional packing material bed different than the feed point, and connected in series (possibly through other sectional packing material beds and/or a unit changing the ion equilibrium) with the sectional packing material bed to which feed solution is supplied.
  • the liquid present in the sectional packing material beds with dry solids profile is recycled in a loop comprising one, two or more sectional packing material beds.
  • eluent is introduced into a sectional packing material bed and a corresponding amount of product fraction or fractions are recovered at a downstream point of the packing material bed, from the same or a downstream sectional packing material bed.
  • a process step comprises one or more of the above simultaneous identical or different phases.
  • a step can consist of, for example, a feeding phase, recycling phase or eluting phase only, a feeding phase and a simultaneous recycling and/or eluting phase or phases, an eluting phase and a simultaneous recycling phase or phases, a recycling phase and a simultaneous eluting phase or phases, etc. These steps are repeated one or several times during the sequence.
  • a sequence comprises 4 to 20, preferably 4 to 10 steps.
  • a sequence comprising the above steps is repeated about 6 to 8 times to equilibrate the system, whereafter the process is continued in a state of equilibrium.
  • a loop may comprise one, two or more sectional packing material beds packed in one or more columns.
  • recycling is employed such that one, two, three or even more discrete successive loops are formed in the recycling phase.
  • the number of sectional packing material beds is three, these may form one loop or preferably two loops (in which case the method is called a two-phase method), one of the loops comprising one and the other two sectional packing material beds.
  • each of these may be closed or open, that is, when the liquid is recycled in one loop, eluent can be introduced into the other loop and a product fraction can be withdrawn there-from.
  • the flow through the packing material beds may be effected between the successive loops, the flows conveying material from one loop to another.
  • each sectional packing material bed may form one discrete loop.
  • a loop may comprise one or more sectional packing material beds.
  • a particularly preferred embodiment of the invention is a simulated moving bed method employing sectional packing material beds in two different ionic forms for simultaneous recovery of xylose and lignosulphonates from a hardwood sulphite cooking liquor on an industrial scale in high yields and advantageous purity for further processing or use. Furthermore, the salts, oligosaccharides and other components in the sulphite cooking liquor which are harmful to the production of pure crystalline xylose, for instance, can be advantageously removed from the xylose fraction by this method. If a softwood sulphite cooking liquor is employed as the raw material, the prevailing monosaccharide is mannose and a mannose-rich fraction is obtained by the method.
  • the method of the invention yields a dry solids profile in which lignosulphonates are concentrated in relation to salts at the front slope of the dry solids profile, and they can be recovered by suitably selecting the product withdrawal point.
  • a monosaccharide e.g. xylose
  • a residue fraction e.g. xylose
  • the method of the invention yields a dry solids profile in which lignosulphonates are concentrated in relation to salts at the front slope of the dry solids profile, and they can be recovered by suitably selecting the product withdrawal point.
  • the implementation of the method e.g. the ionic forms of the sectional packing materials; number of loops to be formed
  • the process parameters are chosen for example in accordance with the composition of the feed solution employed as the raw material so as to yield an optimum result with regard to product purity and yield and the separation capacity of the packing material.
  • a strong acid gel-type cation exchange resin e.g. "Finex”, “Amberlite” or “Dowex"
  • the packing material preferably has the ionic form of the feed solution.
  • the solids present in the solution are removed therefrom by filtration.
  • the solution to be fractionated is e.g. a sulphite cooking liquor, vinasse or molasses
  • it is heated to 40 to 100°C, preferably 50 to 85°C, prior to being fed into the separation process.
  • the eluent employed can be water or a solution obtained from concentration of dilute fractions (e.g. condensate obtained from evaporative concentration) at a temperature 40 to 100°C, preferably 50 to 85°C.
  • the linear flow rate of the liquid in the columns is 0.5 to 12 m/h, even 20 m/h, preferably 2 to 10 m/h.
  • a chromatographic separation apparatus comprising four columns connected in series was employed. Three of these were separation columns and one was a column removing divalent cations.
  • the apparatus further comprised a feed pump, recycle pumps, an eluent water pump, flow and pressure regulators, and inlet and product valves for the process streams.
  • Columns 1, 2 and 4 were separation columns and column 3 a column for removing divalent cations.
  • the two first columns comprised four sectional packing material beds (8 m)
  • the column for removing divalent cations comprised one sectional packing material bed (1.5 m)
  • the fourth column comprised two sectional packing material beds (4 m).
  • Each of the four columns was packed with a strong acid cation exchange resin (Finex V09 CTM).
  • the resin had a polystyrene skeleton; it was cross-linked with divinylbenzene and activated with sulphonic acid groups, and had a mean bead size (in Na + form) of 0.39 mm.
  • the resin had a DVB content of 5.5%.
  • the resin of the first two columns had been regenerated into Ca 2+ form and the sectional packing material of columns 3 and 4 into Na + form prior to the test.
  • the feed solution was hardwood sulphite cooking liquor whose composition was analyzed by HPLC.
  • the cooking liquor was in calcium base form.
  • Table 1 The analysis results are shown in Table 1, where the percentages of the different components are given as per cent by weight on dry solids basis.
  • Fractionation was performed by a four-step sequence.
  • the sequence had a cycle length of 92 minutes, and it comprised the following steps:
  • step 1 After the sequence was carried to completion, the process control program was continued and it returned to the beginning, starting the sequence anew from step 1. By repeating this sequence six to eight times the system was equilibrated. The method was proceeded with in a state of equilibrium, and the progress of the separation process was monitored with a density meter, a meter for optical activity, and a conductivity meter, and the separation was controlled by a microprocessor which controlled precisely the volume flow rates and volumes of feeds, employing quantity/volume measuring devices, temperature controllers, valves and pumps.
  • Example 2 Fractionation was performed employing the chromatographic separation apparatus described in Example 1, which comprised two loops, removal of divalent cations, and pH adjustment.
  • the sequence carried out differed from the procedure of Example 1 in regard to step 2, in which a residue fraction and a recycle fraction were successively eluted with water from column 4.
  • a fraction rich in lignosulphonates was additionally eluted.
  • the volume parameters and volume flow rates of the feeds and recovered fractions were modified. These modifications were due to the fact that a different packing material (Relite C-360) was employed in the column for removal of divalent cations, and the sectional packing material bed in column 4 had a greater height.
  • Relite C-360 packing material
  • the resin Relite C-360TM had a polystyrene skeleton cross-linked with divinylbenzene, and it was activated with sulphonic acid groups; the bead size was 0.3 to 1.2 mm and the DVB content 16%.
  • the sectional packing material in the other columns was the same as in Example 1.
  • the feed solution was the same as above.
  • a lignosulphonate-rich fraction was eluted from column 2.
  • Fractionation was performed by a four-step sequence.
  • the sequence had a length of 98 minutes, and it comprised the following steps:
  • Figure 1 shows the separation curves of column 1
  • Figure 2 the separation curves of column 2
  • Figure 3 the separation curves of column 3 for the removal of divalent cations
  • Figure 4 the separation curves of column 4 for this fractionation.
  • the lignosulphonate content has been determined by means of UV absorbance measurement (absorptivity 14.25 l ⁇ g -1 ⁇ cm -1 ). Analysis of product fractions Xylose Residue 1 Residue 4/1 + recycle Residue 4/2 Lignosulphonate fraction Volume, l 22.0 20.0 37.0 4.0 16 Dry solids content, K-F, g/100 g 16.44 10.07 4.87 10.61 20.40 Xylose, % 70.83 0.64 7.07 24.01 0.29 Monosaccharides, % 81.86 0.89 8.65 28.57 0.29 Oligosaccharides, % 1.51 0.00 1.29 5.37 0.00 Lignosulphonates, % 5.02 57.70 25.60 16.56 65.00 Others 11.61 41.41 64.46 49.50 34.71
  • Fractionation was performed with a chromatographic separation apparatus comprising four columns.
  • the first loop comprised columns 1 and 2 (packing material in Ca 2+ form), column 3 was a column for the removal of divalent cations in the solution, and a pH adjustment unit was connected between column 3 and column 4.
  • Column 4 constituted the latter loop, and its packing material was in the Na + form.
  • the feed solution and the sectional packing material for the columns were the same as in Example 2.
  • Fractionation was performed by a five-step sequence.
  • the sequence had a length of 100 minutes, and it comprised the following steps:
  • the pH of the solution obtained from column 2 and introduced into column 3 was adjusted with sodium hydroxide to about 7 at about 60°C.
  • a quantity of an aqueous solution of sodium sulphite (about 1 M) was added such that the amount of added sulphite ions was about 1.3 times the molar amount of calcium to be precipitated.
  • Kenite 300 diatomaceous earth was employed as an aid in the filtration. Thus it was possible to remove about 90% of the calcium present in the solution. Xylose losses in the calcium removal thus performed were negligible.
  • a pilot plant scale chromatographic test apparatus was used.
  • the apparatus comprised three chromatographic separation columns connected in series, a pH adjustment unit, a filtration unit, a feed pump, recycling pumps, an eluent water pump, flow and pressure regulators, and inlet and product valves for the process streams.
  • Each of the three columns was packed with a strong acid cation exchanged resin (Finex C13 STM).
  • the resin had a polystyrene skeleton, it was cross-linked with divinylbenzene and activated with sulphonic acid groups and had a mean bead size (in Na + form) of 0.36 mm.
  • the resin had a DVB content of 8%.
  • the packing material of columns 1 and 2 was in K + form and column 3 was in Ca 2+ form.
  • the pH adjustment unit and filtration unit were connected between columns 2 and 3.
  • the pH was adjusted with Ca(OH) 2 .
  • the total height of the packing material beds in the two first columns was 10 m, and the height of the packing material bed in the third column was 5 m.
  • the feed solution was vinasse whose composition is shown in Table 5. The percentages of the different components are given as per cent by weight on dry solids basis. Analysis of feed solution Inositol, % 0.4 Glycerol, % 6.3 Betaine, % 13.8 Trisaccharides, % 0.4 Disaccharides, % 1.6 Monosaccharides, % 7.9 Others, % 69.6 Water was used as eluent.
  • Fractionation was performed by an eight-step sequence.
  • the sequence had a cycle length of 93 minutes, and it comprised the following steps:
  • a two-loop apparatus comprising five chromatographic separation columns was used to separate a solution prepared from lactose as follows:
  • the lactose was isomerized by the conventional method with alkali into a lactulose-containing syrup.
  • the resulting syrup was purified in the conventional manner by ion exchange employing ion exchange resins.
  • the lactulose content of the resulting syrup was 22% on dry solids basis.
  • Lactose was crystallized from the ion-exchanged syrup twice, so that the lactulose content of the mother solution obtained was 50% on dry solids basis and the contents of lactose and other components (e.g. galactose) 30% and 20%, respectively.
  • the columns were packed with the same ion exchange resin as in Example 1.
  • the packing material of the three first columns was in Ca 2+ form and the packing material of the two last two columns in Na + form.
  • Fractions enriched with lactose and other components were withdrawn from all three columns having a packing material in Ca 2+ form.
  • the first fraction to be recovered was the lactose fraction, and the last fraction was the fraction enriched with other components (galactose).
  • the lactulose-containing concentrate with average retention was introduced into the packing material having Na + form.
  • a lactose fraction was withdrawn from both columns having a packing material in Na + form, and a fraction enriched with other components (galactose) was withdrawn from the last column (fifth column in the system).
  • the lactulose fraction obtained had a lactulose content of 85% on dry solids basis and a lactose content of 10% on dry solids basis.
  • the combined lactose fractions contained 15% of lactulose on dry solids basis and 74.7% of lactose on dry solids basis.
  • the lactulose and lactose contents of the combined by-product fraction (which comprised mainly galactose) were 22% and 18.8% on dry solids basis, respectively.
  • a two-loop apparatus comprising five chromatographic separation columns was used to separate a synthetic maltose-containing syrup containing also glucose and fructose.
  • the solution contained 20% of maltose, 40% of glucose and 40% of fructose, all calculated on dry solids basis.
  • the columns were packed with the same ion exchange resin as in Example 1.
  • the packing material of the first column was in Na + form and the packing material of the next four columns in Ca 2+ form.
  • a maltose fraction was withdrawn from the first column, and a glucose-fructose-containing concentrate was introduced into the packing material having Ca 2+ form.
  • a glucose fraction and a fructose fraction were withdrawn from the third and fifth column having a packing material in Ca 2+ form (the fructose fraction was eluted more slowly).
  • the withdrawn maltose fraction contained 90% of maltose on dry solids basis and 10% of glucose on dry solids basis.
  • the combined glucose fractions contained 3% of maltose and 95% of glucose, and the combined fructose fractions contained 1% of maltose and 99% of fructose (all on dry solids basis).
  • Cane molasses was softened and clarified in the conventional manner by phosphatization treatment and by removing the resulting solids by centrifugation. After the centrifugation, the solution was subjected to filtration with diatomaceous earth as an aid.
  • a two-loop apparatus comprising seven columns was used to separate cane molasses thus pretreated, which contained 30% of non-sugars, 40% of sucrose, 15% of glucose and 15% of fructose.
  • the packing material of the first three columns was in Na + ,K + form (in equilibrium with cations in the molasses), and the packing material of the other four columns of the apparatus was in Ca 2+ form.
  • a non-sugar fraction was withdrawn from all three columns and a sucrose fraction with average retention was withdrawn from the third column, having a packing material in Na + ,K + form.
  • the glucose-fructose-containing concentrate which was the slowest to elute was introduced into the packing material having Ca 2+ form.
  • a glucose fraction and a fructose fraction were withdrawn from the fifth and seventh column having a packing material in Ca 2+ form.
  • the combined non-sugar fractions withdrawn contained 85% of non-sugars and 15% of sucrose; the sucrose fraction obtained contained 10% of non-sugars and 85% of sucrose (all on dry solids basis).
  • the glucose fractions obtained contained 96% of glucose and 2% of fructose on dry solids basis; the fructose fractions contained 95.6% of fructose and 2% of glucose.

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  • General Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Zoology (AREA)
  • Sustainable Development (AREA)
  • Treatment Of Liquids With Adsorbents In General (AREA)
  • Steroid Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Saccharide Compounds (AREA)
EP95915913A 1994-04-21 1995-04-19 Method for fractionating a solution Expired - Lifetime EP0756511B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FI941866A FI98791C (fi) 1994-04-21 1994-04-21 Menetelmä liuoksen fraktioimiseksi
FI941866 1994-04-21
PCT/FI1995/000224 WO1995029002A1 (en) 1994-04-21 1995-04-19 Method for fractionating a solution

Publications (2)

Publication Number Publication Date
EP0756511A1 EP0756511A1 (en) 1997-02-05
EP0756511B1 true EP0756511B1 (en) 1999-12-15

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EP95915913A Expired - Lifetime EP0756511B1 (en) 1994-04-21 1995-04-19 Method for fractionating a solution

Country Status (19)

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US (1) US5730877A (da)
EP (1) EP0756511B1 (da)
JP (1) JP3903266B2 (da)
KR (1) KR100372962B1 (da)
AT (1) ATE187657T1 (da)
AU (1) AU2260795A (da)
CA (1) CA2188262C (da)
DE (1) DE69513966T2 (da)
DK (1) DK0756511T3 (da)
ES (1) ES2141931T3 (da)
FI (1) FI98791C (da)
GR (1) GR3032860T3 (da)
HU (1) HU216319B (da)
PT (1) PT756511E (da)
RU (1) RU2136345C1 (da)
TW (1) TW351678B (da)
UA (1) UA39135C2 (da)
WO (1) WO1995029002A1 (da)
ZA (1) ZA953242B (da)

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US5795398A (en) 1994-09-30 1998-08-18 Cultor Ltd. Fractionation method of sucrose-containing solutions
FI97625C (fi) * 1995-03-01 1997-01-27 Xyrofin Oy Menetelmä ksyloosin kiteyttämiseksi vesiliuoksista
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FI102962B1 (fi) * 1996-06-24 1999-03-31 Xyrofin Oy Menetelmä ksylitolin valmistamiseksi
AU6043598A (en) 1997-01-29 1998-08-18 Amalgamated Research, Inc. Method of displacement chromatography
EP0960641A4 (en) * 1997-09-22 2002-02-20 Organo Corp METHOD AND DEVICE FOR CHROMATOGRAPHIC SEPARATION
FI974625A0 (fi) * 1997-12-23 1997-12-23 Xyrofin Oy Foerfarande foer framstaellning av xylos
JP3478325B2 (ja) * 1997-12-25 2003-12-15 オルガノ株式会社 クロマト分離方法
FI117465B (fi) 2000-02-03 2006-10-31 Danisco Sweeteners Oy Menetelmä pureskeltavien ytimien kovapinnoittamiseksi
GB0022713D0 (en) * 2000-09-15 2000-11-01 Xyrofin Oy Method for fractionating liquid mixtures
FI111960B (fi) 2000-12-28 2003-10-15 Danisco Sweeteners Oy Erotusmenetelmä
JP4756232B2 (ja) * 2000-12-28 2011-08-24 ダニスコ スイートナーズ オイ 分離プロセス
CN1250733C (zh) * 2001-04-20 2006-04-12 纳幕尔杜邦公司 一种用于生物发酵系统的产物收取方法
FI20010977A (fi) * 2001-05-09 2002-11-10 Danisco Sweeteners Oy Kromatografinen erotusmenetelmä
US20040173533A1 (en) * 2001-07-24 2004-09-09 Farone William A. Separation of xylose and glucose
US7566556B2 (en) * 2002-03-01 2009-07-28 Academia Sinica Enhancing enzyme thermostability by mixing with sorghum liquor waste
FI20020592A (fi) * 2002-03-27 2003-09-28 Danisco Sweeteners Oy Menetelmä sokereiden, sokerialkoholien, hiilihydraattien ja niiden seosten erottamiseksi niitä sisältävistä liuoksista
DK2316551T3 (da) * 2003-02-25 2013-01-02 Dupont Nutrition Biosci Aps Simulated Moving Bed- (SMB) system
US20060251761A1 (en) * 2005-05-03 2006-11-09 Robert Jansen Grain wet milling process for producing dextrose
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US9109265B2 (en) * 2008-06-26 2015-08-18 Dupont Nutrition Biosciences Aps Process for separation of Ca- or Mg-sulfite spent liquor to yield crystalline xylose
DK2401046T3 (da) 2009-02-25 2020-08-03 Dupont Nutrition Biosci Aps Separationsfremgangsmåde
EP2292803B1 (en) 2009-07-07 2013-02-13 DuPont Nutrition Biosciences ApS Separation process
CN102946961B (zh) * 2010-03-30 2015-11-25 杜邦营养生物科学有限公司 分离方法
CN103201395B (zh) 2010-06-26 2016-03-02 威尔迪亚有限公司 糖混合物及其生产和使用方法
IL206678A0 (en) 2010-06-28 2010-12-30 Hcl Cleantech Ltd A method for the production of fermentable sugars
IL207329A0 (en) 2010-08-01 2010-12-30 Robert Jansen A method for refining a recycle extractant and for processing a lignocellulosic material and for the production of a carbohydrate composition
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Also Published As

Publication number Publication date
GR3032860T3 (en) 2000-07-31
DE69513966T2 (de) 2000-05-04
UA39135C2 (uk) 2001-06-15
ZA953242B (en) 1996-01-18
RU2136345C1 (ru) 1999-09-10
ATE187657T1 (de) 2000-01-15
EP0756511A1 (en) 1997-02-05
PT756511E (pt) 2000-04-28
KR970702093A (ko) 1997-05-13
FI941866A (fi) 1995-10-22
KR100372962B1 (ko) 2003-04-21
HU216319B (hu) 1999-06-28
WO1995029002A1 (en) 1995-11-02
FI941866A0 (fi) 1994-04-21
JPH09511946A (ja) 1997-12-02
US5730877A (en) 1998-03-24
FI98791B (fi) 1997-05-15
HUT75293A (en) 1997-05-28
FI98791C (fi) 1997-08-25
CA2188262C (en) 2006-08-29
HU9602906D0 (en) 1996-12-30
JP3903266B2 (ja) 2007-04-11
ES2141931T3 (es) 2000-04-01
DE69513966D1 (de) 2000-01-20
TW351678B (en) 1999-02-01
CA2188262A1 (en) 1995-11-02
DK0756511T3 (da) 2000-05-01
AU2260795A (en) 1995-11-16

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